The present invention relates to cationic aminodianthraquinones containing at least one cationic group Z, with Z being chosen from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring, and aliphatic chains containing at least one quaternized unsaturated ring, their use as direct dyes in applications for dyeing keratinous materials, such as human keratinous fibers, for example hair, the dyeing compositions containing them, as well as the dyeing methods using them.
It is known to dye keratinous fibers, and in particular hair, with dyeing compositions containing direct dyes. Direct dyes are dye molecules having affinity for keratinous fibers. The dyeing method which uses them is a so-called direct dyeing method which comprises allowing the direct dyes to act on the fibers, and subsequently rinsing the fibers.
The colors resulting therefrom are temporary or semipermanent colors, because the nature of the interactions which links the direct dyes to the keratinous fiber, and their desorption from the surface and/or the core of the fiber are responsible for their weak dyeing power, and their poor resistance to washings and perspiration.
Cationic aminoanthraquinones have already been described among the known direct dyes. Such aminoanthraquinones are described in, for example, French Patent Nos. 1,422,016 (and its addition 87,902), 1,391,675, 1,401,163, 1,379,649, 1,430,089, 1,584,965, 2,050,397, 2,548,895, U.S. Pat. Nos. 5,169,403, 5,314,505, 5,486,629, 5,520,707, and European Patent Nos. 818,193 and 852,136, and contain only one anthraquinone nucleus.
However, in hair dyeing, direct dyes are being continually sought which exhibit increasingly better characteristics.
It is thus after major research studies carried out on this subject that the inventors have discovered a new class of cationic aminoanthraquinones, the cationic aminodianthraquinones containing at least one cationic group Z, with Z being chosen from quaternized aliphatic chains, aliphatic chains containing at least one quaternized saturated ring, and aliphatic chains containing at least one quaternized unsaturated ring.
This new family of dyes can exhibit the very advantageous characteristic feature of greater solubility in the dyeing media. These new dyes can also generate colors, by direct dyeing, having an intensity and a resistance to various attacks to which the hair may be subjected: light, adverse weather conditions, shampoos, and perspiration, which is substantially improved compared with that of the colors produced with known prior art cationic aminoanthraquinones.
This discovery forms the basis of the present invention.
A subject of the present invention is thus the aminodianthraquinones of formula (I) 
in which formula,
B is a linking chosen from a linear or branched alkyl chain preferably containing 1 to 14 carbon atoms, which may be interrupted by one or more groups Z, defined below, one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, or a mixture of one or more groups Z and one or more heteroatoms; and which may be unsubstituted or substituted with one or more hydroxyl or C1-C6 alkoxy radicals, and which may carry one or more ketone functions;
R1, R2, R3, R4, Rxe2x80x21, Rxe2x80x22, Rxe2x80x23 and Rxe2x80x24, which may be identical or different, are chosen from one of the two valencies of a linking arm B; a hydrogen atom; a halogen atom; a group Z, defined below; a (C1-C6)alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a cyano radical; a nitro radical; a carboxyl radical; a carbamyl radical; a sulpho radical; a substituted or unsubstituted amino radical, having the same meanings as NHR5 or NHRxe2x80x25 defined below, and which may be identical or different; a group OR6 or SR6 or ORxe2x80x26 or SRxe2x80x26 defined below; R5 and Rxe2x80x25, which may be identical or different, are chosen from one of the two valencies of a linking arm B; a hydrogen atom; a group Z, defined below; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a (C1-C6)alkoxy(C1-C6 alkyl) radical; an aryl radical; a benzyl radical; a cyano(C1-C6 alkyl) radical; a carbamyl(C1-C6 alkyl) radical; an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical; a thiocarbamyl(C1-C6 alkyl) radical; a trifluoro(C1-C6 alkyl) radical; a sulpho(C1-C6 alkyl) radical; a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical; a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical; an aminosulphonyl(C1-C6 alkyl) radical; an N-Z-aminosulphonyl(C1-C6 alkyl) radical; an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical; a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical; an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical; an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical, and wherein the amine is substituted with at one or two radicals, identical or different, chosen from the C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, carbamyl, N-(C1-C6)alkylcarbamyl or N, N-di(C1-C6)alkylcarbamyl, (C1-C6)alkylsulphonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, and thiocarbamyl radicals, or from the group Z, defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing carbon or containing at least one heteroatom;
R6 and Rxe2x80x26, which may be identical or different, are chosen from one of the two valencies of a linking arm B; a hydrogen atom; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a group Z, defined below; a (C1-C6)alkoxy(C1-C6 alkyl) radical;
an aryl radical; a benzyl radical; a carboxy(C1-C6 alkyl) radical; a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical; a cyano(C1-C6 alkyl) radical; a carbamyl(C1-C6 alkyl) radical; an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical; an N,N-di(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical; a trifluoro(C1-C6 alkyl) radical; an aminosulphonyl(C1-C6 alkyl) radical; an N-Z-aminosulphonyl(C1-C6 alkyl) radical; an N-(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical; an N,N-di(C1-C6)alkylaminosulphonyl(C1-C6 alkyl) radical; a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical; a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical; a (C1-C6)alkylcarbonyl(C1-C6 alkyl) radical; an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical; an amino(C1-C6 alkyl) radical, wherein the alkyl is unsubstituted or substituted with at least one hydroxyl radical, and wherein the amine is substituted with one or two radicals, identical or different, chosen from the C1-C6 alkyl, monohydroxy(C1-C6 alkyl), polyhydroxy(C2-C6 alkyl), (C1-C6)alkylcarbonyl, formyl, trifluoro(C1-C6)alkylcarbonyl, (C1-C6)alkylcarboxyl, carbamyl, N-(C1-C6)alkylcarbamyl, N,N-di(C1-C6)alkylcarbamyl, thiocarbamyl, and (C1-C6)alkylsulphonyl radicals, the groups Z, defined below, or which may form, together with the nitrogen atom to which they are attached, a 5- or 6-membered ring containing carbon or containing at least one heteroatom;
Z is chosen from the unsaturated cationic groups of the formulae (11) and (111), and the saturated cationic groups of the formula (IV): 
xe2x80x83in which:
D is a linking arm chosen from linear and branched alkyl chains, preferably containing from 1 to 14 carbon atoms, which may be interrupted by one or more heteroatoms such as oxygen, sulphur or nitrogen, and which may be substituted with at least one radical chosen from hydroxyl and C1-C6 alkoxy, and which may carry at least one ketone function;
the members E, G, J, L and M, which are identical or different, are chosen from carbon, oxygen, sulphur and nitrogen atoms;
n is an integer ranging from 0 to 4;
m is an integer ranging from 0 to 5;
the radicals R, which are identical or different, are chosen from one of the two valencies of a linking arm B, a second group Zxe2x80x2, which has the same definition as the group Z, and which is identical or different from the first group Z; a halogen atom; a hydroxyl radical; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a nitro radical; a cyano radical; a cyano(C1-C6 alkyl) radical; a C1-C6 alkoxy radical; a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical; an amido radical; an aldehydo radical; a carboxyl radical; a C1-C6 alkylcarbonyl radical; a thio radical; a thio(C1-C6 alkyl) radical; a (C1-C6)alkylthio radical; an amino radical; an amino radical protected with a (C1-C6)alkylcarbonyl, carbamyl or (C1-C6)alkylsulphonyl radical; a group NHRxe2x80x3 or NRxe2x80x3Rxe2x80x2xe2x80x3, wherein Rxe2x80x3 and Rxe2x80x2xe2x80x3, which are identical or different, are chosen from a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical and a polyhydroxy(C2-C6 alkyl) radical;
R7 is chosen from one of the two valencies of a linking arm B; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a cyano(C1-C6 alkyl) radical; a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical; a (C1-C6)alkoxy(C1-C6 alkyl) radical; a carbamyl(C1-C6 alkyl) radical; a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical; a benzyl radical, and a second group Zxe2x80x2, which has the same definition as the group Z, which is identical or different from the group Z;
R8, R9 and R10, which are identical or different, are chosen from one of the two valencies of a linking arm B; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; a (C1-C6)alkoxy(C1-C6 alkyl) radical; a cyano(C1-C6 alkyl) radical; an aryl radical; a benzyl radical; an amido(C1-C6 alkyl) radical; a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical; an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl; two of the radicals R8, R9 and R10 may also form, together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered ring containing carbon or capable of containing at least one heteroatom such as, for example, a pyrrolidine ring, a piperidine ring, a piperazine ring or a morpholine ring, it being possible for the ring to be unsubstituted or substituted with a substituent selected from a halogen atom, a hydroxyl radical, a C1-C6 alkyl radical, a monohydroxy(C1-C6 alkyl) radical, a polyhydroxy(C2-C6 alkyl) radical, a nitro radical, a cyano radical, a cyano(C1-C6 alkyl) radical, a C1-C6 alkoxy radical, a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical, an amido radical, an aldehydo radical, a carboxyl radical, a keto(C1-C6 alkyl) radical, a thio radical, a thio(C1-C6 alkyl) radical, a (C1-C6)alkylthio radical, an amino radical, an amino radical protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl; one of the radicals R8, R9 and R10 may also be chosen from the group Zxe2x80x2, having the same definition as the group Z, and which is identical or different from the group Z;
R11 is chosen from one of the two valencies of a linking arm B; a C1-C6 alkyl radical; a monohydroxy(C1-C6 alkyl) radical; a polyhydroxy(C2-C6 alkyl) radical; an aryl radical; a benzyl radical; an amino(C1-C6 alkyl) radical, an amino(C1-C6 alkyl) radical, wherein the amine is protected with a radical chosen from (C1-C6)alkylcarbonyl, carbamyl, and (C1-C6)alkylsulphonyl; a carboxy(C1-C6 alkyl) radical; a cyano(C1-C6 alkyl) radical; a carbamyl(C1-C6 alkyl) radical; a trifluoro(C1-C6 alkyl) radical; a tri(C1-C6)alkylsilane(C1-C6 alkyl) radical; a sulphonamido(C1-C6 alkyl) radical; a (C1-C6)alkylcarboxy(C1-C6 alkyl) radical; a (C1-C6)alkylsulphinyl(C1-C6 alkyl) radical; a (C1-C6)alkylsulphonyl(C1-C6 alkyl) radical; a (C1-C6)alkylketo(C1-C6 alkyl) radical; an N-(C1-C6)alkylcarbamyl(C1-C6 alkyl) radical; an N-(C1-C6)alkylsulphonamido(C1-C6 alkyl) radical;
x and y are the integers 0 or 1; with the following conditions:
in the unsaturated cationic groups of formula (II):
when x is 0, the linking arm D is attached to the nitrogen atom;
when x is 1, the linking arm D is attached to one of the members E, G, J or L,
y is 1:
1) when the members E, G, J and L are simultaneously a carbon atom, and R7 is carried by the nitrogen atom of the unsaturated ring; or
2) when at least one of the members E, G, J and L is a nitrogen atom onto which the radical R7 is attached;
in the unsaturated cationic groups of formula (III):
when x is 0, the linking arm D is attached to the nitrogen atom;
when x is 1, the linking arm D is attached to one of the members E, G, J, L or M;
y is 1 when at least one of the members E, G, J, L and M is a divalent atom, and R7 is carried by the nitrogen atom of the unsaturated ring;
in the cationic groups of formula (IV):
if x is 0, then the linking arm D is attached to the nitrogen atom carrying the radicals R8 to R10,
if x is 1, then two of the radicals R8 to R10 conjointly form with the nitrogen atom to which they are attached a saturated 5- or 6-membered ring as defined above; and the linking arm D is carried by a carbon atom of the said saturated ring;
Xxe2x88x92 is chosen from monovalent and divalent anions; in one embodiment of the invention, X chosen from (i) a halogen atom such as chlorine, bromine, fluorine and iodine, (ii) a hydroxide, (iii) a hydrogen sulphate, and (iv) a (C1-C6)alkylsulphate such as, for example, methyl sulphate and ethyl sulphate;
it being understood that:
(i) the number of cationic groups Z is at least equal to 1,
(ii) the formula (I) does not designate the compounds of the formula (VI): 
in which
R1xe2x80x3, R2xe2x80x3, R3xe2x80x3 and R4xe2x80x3, which are identical or different, are chosen from a hydrogen atom, a halogen atom, an alkyl radical, and a hydroxyl radical,
R5xe2x80x3 is chosen from a hydrogen atom and an alkyl radical,
R8xe2x80x3 and R9xe2x80x3, which are identical or different, are chosen from an alkyl radical, a mono- or polyhydroxyalkyl radical, and an aryl radical,
D has the same meanings as in formula (I),
Xxe2x88x92 designates an anion.
In the above formulae (I), (II), (III) and (IV), the alkyl and alkoxy radicals may be linear or branched.
The compounds of formula (I) may be optionally salified with strong inorganic acids such as HCl, HBr, and H2SO4, or organic acids such as acetic, tartaric, lactic, citric and succinic acids.
Examples of the rings of the unsaturated groups Z of formula (II), above, include the pyrrole, imidazole, pyrazole, oxazole, thiazole, and triazole rings.
The rings of the unsaturated groups Z of formula (III), above, may be, for example, the pyridine, pyrimidine, pyrazine, oxazine and triazine rings.
In one embodiment of invention, the cationic aminodianthraquinones of formula (I) are chosen from the compounds of the formulae (I)2 to (I)12: 
The cationic aminodianthraquinones of formula (I) in accordance with the invention can be easily obtained, according to generally well known state of the art methods and in particular, for example, by:
condensation of two anthraquinone molecules containing a haloalkyl radical with a molecule of a compound carrying two tertiary amine radicals separated by a linking arm B as defined in formula (I) described above, or alternatively,
condensation of two anthraquinone molecules containing a tertiary amine radical with a molecule of a compound carrying two halogen radicals separated by a linking arm B as defined in formula (I) described above, or alternatively,
(a) condensation of an anthraquinone molecule containing a tertiary amine radical with a molecule of a compound carrying two halogen radicals separated by a linking arm B as defined in formula (I) described above, and
(b) condensation of a second anthraquinone molecule different from the first and also containing a tertiary amine radical, or alternatively,
(a) condensation of an anthraquinone molecule carrying a haloalkyl radical with a molecule of a compound carrying two tertiary amine radicals separated by a linking arm B as defined in formula (I) described above, and
(b) condensation of a second anthraquinone molecule different from the first and also carrying a haloalkyl radical, or alternatively,
condensation of an anthraquinone molecule containing a tertiary amine radical with an anthraquinone molecule containing a haloalkyl radical.
The quaternization step is generally, for the sake of convenience, the last step in the synthesis, but may occur earlier in the sequence of reactions leading to the preparation of the compounds of formula (I).
A subject of the invention is also dyeing compositions for keratinous materials, comprising, in a medium appropriate for dyeing, an effective quantity for dyeing keratinous materials of at least one cationic 
aminodianthraquinone as defined above by formula (I).
Another subject of the invention is compositions for the direct dyeing of human keratinous fibers such as hair, characterized in that it comprises, in a medium appropriate for dyeing, an effective quantity for dyeing keratinous fibers of at least one cationic aminodianthraquinone as defined above by formula (I).
Another subject of the invention is the use of cationic aminodianthraquinones of formula (I), for which B, R1, R2, R3, R4, R5, Rxe2x80x21, Rxe2x80x22, Rxe2x80x23, Rxe2x80x24 and Rxe2x80x25 have the same meanings as previously described, it being understood that the number of cationic groups Z is at least equal to 1, as direct dyes, in, or for the preparation of, dyeing compositions for keratinous materials, for example human keratinous fibers such as hair.
However other characteristics, aspects and advantages of the invention will emerge even more clearly on reading the description which follows, as well as the various concrete, but not at all limiting, examples intended to illustrate it.
In one embodiment of the dyeing compositions in accordance with the invention, the amount of the at least one cationic aminodianthraquinone(s) of formula (I), or an addition salt thereof, in the dyeing composition ranges from about 0.005 to about 12%, relative to the total weight of the dyeing composition. In another embodiment, the amount of the at least one aminodianthraquinone, or the acid addition salt thereof, ranges from about 0.05 to about 6% by weight, relative to the total weight of the composition.
The cationic aminodianthraquinones of formula (I) in accordance with the invention may also serve, in the well-known oxidation dyeing methods, using oxidation dyes (oxidation dye precursors and optionally couplers), to give the colors obtained with the oxidation dyes different shades or increase their shimmer.
In order to obtain a variety of colors, the dyeing composition according to the invention may also contain, in addition to the cationic aminodianthraquinones of formula (I), at least one additional direct dye that is conventionally used in the art. Examples of the at least on additional direct dye include:
nitrophenylenediamines, nitrodiphenylamines, nitroanilines, nitrophenol ethers, nitrophenols, and nitropyridines; and
other anthraquinone dyes different from those in accordance with the present invention; and
mono- or diazo, triarylmethane, azine, acridine and xanthene dyes; and
metal-containing dyes.
The total amount of all these other direct addition dyes in the composition according to the present invention may range from about 0.5 to about 10% by weight, relative to the total weight of the dyeing composition.
The medium (or carrier) appropriate for dyeing is generally water or a mixture of water and at least one organic solvent for solubilizing the compounds which would not be sufficiently soluble in water. Examples of organic solvents include lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether; as well as aromatic alcohols, such as benzyl alcohol or phenoxyethanol; and similar products and mixtures thereof.
In one embodiment of the invention, the solvents may be present in an amount ranging from approximately 1 to approximately 40% by weight, relative to the total weight of the dyeing composition. In another embodiment of the invention, the amount of solvents may range from approximately 5 to approximately 30% by weight, relative to the total weight of the dyeing composition. It is also possible to add to the composition according to the invention fatty amides such as mono- and diethanolamides of acids derived from copra, lauric acid and oleic acid, in amounts ranging from about 0.05 to about 10% by weight, relative to the total weight of the composition.
It is also possible to add to the composition according to the invention well-known state of the art surfactants of the anionic, cationic, nonionic, amphoteric or zwitterionic type, or mixtures thereof. In one embodiment of the invention, the surfactants can be present in an amount ranging from about 0.1 to about 50% by weight, relative to the total weight of the composition. In another embodiment of the invention, the surfactants can be present in an amount ranging from about 1 to about 20% by weight, relative to the total weight of the composition.
It is also possible to use thickening agents in a proportion ranging from about 0.2 to about 5%.
The dyeing composition according to the invention may contain, in addition, various customary adjuvants such as antioxidants, perfumes, sequestering agents, dispersing agents, hair conditioners, preservatives, and opacifying agents, as well as any other adjuvant normally used in dyeing keratinous materials.
Of course, persons skilled in the art will be careful to choose the optional additional compound(s) mentioned above such that the advantageous properties intrinsically attached to the dyeing composition according to the invention are not, or not substantially, adversely modified by the addition(s) envisaged.
The pH of the dyeing composition in accordance with the invention may vary between approximately 3 and approximately 12. In one embodiment of the invention, the pH varies between approximately 5 and approximately 11. The pH can be adjusted to the desired value by means of acidifying or alkalinizing agents normally used in dyeing keratinous fibres.
Among the acidifying agents, there may be mentioned, by way of example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, and sulphonic acids.
Suitable alkalinizing agents include ammonium hydroxide, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines, as well as their derivatives, sodium and potassium hydroxides, and the compounds of the formula (V): 
in which W is a propylene residue which is unsubstituted or substituted with a group chosen from a hydroxyl group and a C1-C6 alkyl radical; R12, R13, R14 and R15, which are identical or different, are chosen from a hydrogen atom, a C1-C6 alkyl radical, and a hydroxy(C1-C6 alkyl) radical.
The dyeing composition according to the invention may be provided in various forms, such as in the form of liquids, creams, gels or in any other form appropriate for dyeing keratinous fibers, and more particularly human keratinous fibers and in particular hair. In particular, it can be packaged under pressure in an aerosol can in the presence of a propellant and can form a foam.
Another subject of the present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as hair, by direct dyeing, comprising allowing a dyeing composition containing at least one cationic aminodianthraquinone of formula (I) to act on dry or wet keratinous fibers. It is possible to use the composition according to the invention as a leave-in composition, that is to say that after applying the composition to the fibers, they are dried without intermediate rinsing.
In one embodiment, the process comprises allowing the composition to act on the fibers for an exposure time ranging from approximately 3 to approximately 60 minutes, rinsing the fibers, optionally washing the fibers, and rinsing the fibers again and drying the fibers. In another embodiment of the invention, the process is similar to that just described, except that the exposure time ranges from approximately 5 to approximately 45 minutes.
Concrete and nonlimiting examples illustrating the invention will now be given.